CN102828107B - Preparation method and device for Ln(Fe,M)13 series magnetic refrigeration materials - Google Patents
Preparation method and device for Ln(Fe,M)13 series magnetic refrigeration materials Download PDFInfo
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- CN102828107B CN102828107B CN201210371325.1A CN201210371325A CN102828107B CN 102828107 B CN102828107 B CN 102828107B CN 201210371325 A CN201210371325 A CN 201210371325A CN 102828107 B CN102828107 B CN 102828107B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to a preparation method and device for Ln(Fe,M)13 series magnetic refrigeration materials. According to the practical application requirement of a refrigerator, an alloy as a cast condition is processed into a flake sample with specified dimension and shape, the flake sample is placed into an induction heating device, argon is filled for shielding after vacuumizing, and appropriate frequency and power are selected for carrying out induction heating. Heat input is controlled, thus material temperature is maintained to be in a 1:13 phase forming temperature interval. After set time is up, heating is stopped, and the Ar gas is introduced for cooling, thus the 1:13 phase Ln(Fe,M)13 series magnetic refrigeration materials can be obtained. According to the invention, a self-heating manner is adopted for heating, the sample is uniformly heated, temperature and time are accurate and controllable, heating rate is high, energy conversion efficiency is high, and energy is saved; the obtained sample has higher mechanical properties, is unbreakable and has small grain size; and the preparation method and device disclosed by the invention are applicable to treatment on the flake sample, and the problem that the Ln(Fe,M)13 series magnetic refrigeration materials are difficult to be subjected to machining as the material is brittle after being formed into phase can be effectively solved.
Description
Technical field
The present invention relates to magnetic refrigerating material preparing technical field, particularly Ln (Fe, M)
13be preparation method and the device of magnetic refrigerating material.
Background technology
Magnetic Refrigeration Technique realizes refrigeration by means of the magneto-caloric effect of magneticsubstance, has energy-efficient, environmental protection and the advantage such as reliable and stable, is a kind of green refrigeration technology, has very wide application prospect.
In existing magnetic refrigerating material, there is NaZn
13the Ln (Fe, M) of type phase structure
13be magnetic refrigerating material (being called for short 1:13 phase), with its excellent magnetic heating performance, the prices of raw and semifnished materials are cheap in addition, nontoxic, and are acknowledged as the magnetic refrigerating material (CN101748326A) having practical value most at present.
But owing to becoming mechanism mutually to limit, under conventional preparation process condition, 1:13 is difficult to directly form from as cast condition mutually, often needs alloy cast ingot at high temperature to carry out long-time vacuum heat treatment (CN1450190A).Even so, be also difficult to ensure the uniform component of 1:13 phase, thereby cause the inequality of material monolithic magnetic property.In addition, long heat treatment also can cause abnormal grain growth, causes material fragility to increase, and is difficult to machine-shaping, conventionally can only use with particulate state form, and material use efficiency is low, and material is in use easy to efflorescence, and this is very unfavorable for practical application.
Although adopt the annealing of melt-spun method+short time high temperature can make the heat treatment time that obtains 1:13 phase significantly shorten (CN100567543C), owing to existing prepared material to be the shortcoming such as thin ribbon shaped, easy efflorescence, be difficult to meet application demand.
Summary of the invention
In order to address the above problem, the object of this invention is to provide one and can realize coolingly fast, greatly simplify preparation section, and solve preferably Ln (Fe, M)
13be magnetic refrigerating material Cheng Xianghou is difficult to carry out mechanical workout problem Ln (Fe, M) because material becomes fragile
13be preparation method and the device of magnetic refrigerating material.
Technical scheme of the present invention is: one is prepared Ln (Fe, M)
13be the method for magnetic refrigerating material, specifically comprise following technique: by thickness sheet Ln (Fe, M) between 0.5 ~ 2mm
13be magnetic refrigerating material, adopt pulse heating mode, vacuumize, when vacuum tightness reaches 2.0 × 10
-3pa, is filled with argon shield, is 60Hz-500kHz in frequency, and power is 10kW-100kW, conduction time T
1=2-20s, power-off time T
2=1-8s, heating 10-60 minute, logical argon gas is cooling, obtains the sheet Ln (Fe, M) with 1:13 phase
13it is magnetic refrigerating material.
Another object of the present invention is to provide above-mentioned preparation Ln (Fe, M)
13be the device of magnetic refrigerating material, this device comprises induction heating device, sample chamber, vacuum unit and argon bottle;
Wherein, described sample chamber is placed in induction heating device, one end of described sample chamber be connected with described vacuum unit by vacuum valve, the other end is connected with described argon bottle by argon gas inflation valve, is also provided with tensimeter for monitoring gaseous tension in sample chamber and the safety valve for relief pressure on described sample chamber.
Principle of the present invention is: the heat heating as cast condition Ln (FeM) that utilizes eddy current to produce
13be magnetic refrigerating material, by controlling heat input, make material temperature remain on 1:13 and coordinate in phase temperature range, reach after the specified time, stop heating, lead to Ar air cooling but, thereby obtain 1:13 phase structure.
The key character of the method is, before induction heating, can be according to the requirement of refrigerator practical application, cast alloy is processed into the laminar sample of specified dimension, shape, due within thickness of sample is controlled at the penetration depth scope of surface action, sample can be realized diathermanous formula heating, contributes to ensure into the homogeneity of phase.After heat-processed finishes, because sample is laminar, passing into argon gas can be cooling fast.In addition, for ensureing the security of sample chamber, safety valve 6 is set, in the time that sample chamber internal gas pressure exceedes set(ting)value, i.e. automatic relief pressure.Cooling link after this setting is particularly conducive to heat-processed and finishes, is conducive to ensure the mobility of sample indoor gas, thereby strengthens cooling.
This patent can meet all kinds of Ln (Fe, M)
13be the preparation demand of magnetic refrigerating material, wherein, Ln can be one or more in La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb etc., M can be Al, Co, Si, Mn, Ni etc. one or more.In addition also can meet, all kinds of Ln (Fe, M) of doping C, B
13it is the preparation demand of magnetic refrigerating material.
Beneficial effect of the present invention:
(1) adopt electromagnetic induction principle direct heating, belong to autothermal heating, sample is heated evenly, and Heating temperature and heat-up time are accurately controlled, have heat-up rate fast, and effciency of energy transfer is high, the distinguishing feature of save energy;
(2) become phase at the mutually critical warm area of 1:13, speed is fast, and the time is short, and sample purity is high, and in addition, grain-size is little, and the sample that obtains has compared with high-mechanical property, is difficult for broken;
(3) be particularly suitable for the processing of sheet sample, efficiently solve Ln (Fe, M)
13it is magnetic refrigerating material Cheng Xianghou is difficult to carry out mechanical workout problem because material becomes fragile.
Brief description of the drawings
Fig. 1 is that the present invention prepares Ln (Fe, M)
13it is the structural representation of the device of magnetic refrigerating material.
Fig. 2 magnetic refrigerating material LaFe
10.8co
0.7si
1.5as cast condition sample microtexture photo schematic diagram.
Fig. 3 magnetic refrigerating material LaFe
10.8co
0.7si
1.5the microtexture photo schematic diagram of sample after induction heating.
Fig. 4 magnetic refrigerating material LaFe
10.8co
0.7si
1.5c
0.2as cast condition sample microtexture photo schematic diagram.
Fig. 5 magnetic refrigerating material LaFe
10.8co
0.7si
1.5c
0.2the microtexture photo schematic diagram of sample after induction heating.
Fig. 6 magnetic refrigerating material LaFe
10.8co
0.7si
1.5c
0.2the microtexture photo schematic diagram of sample after induction heating.
In figure:
1. induction heating device, 2. sample chamber, 3. sample, 4 argon gas inflation valves, 5. tensimeter, 6. safety valve, 7. vacuum valve, 8. vacuum unit, 9 argon bottles.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is described further.
As shown in Figure 1, for the present invention prepares Ln (Fe, M)
13it is the device of magnetic refrigerating material.This device comprises induction heating device 1, sample chamber 2, vacuum unit 8 and argon bottle 9;
Wherein, sample chamber 2 is placed in induction heating device 1, one end of sample chamber 2 be connected with vacuum unit 8 by vacuum valve 7, the other end is connected with described argon bottle 9 by argon gas inflation valve 4, for monitoring the tensimeter 5 of gaseous tension in sample chamber and for the safety valve 6 of relief pressure, sample chamber 2 being set.
When use, sheet sample 3 is put into sample chamber 2, make sample length direction parallel with inducedmagnetic field direction.Open vacuum valve 7, vacuumize, when vacuum tightness reaches 2.0 × 10
-3when Pa, close vacuum valve 7, open argon gas valve 4, be filled with argon gas, change by tensimeter 5 detecting pressure, make sample chamber internal gas pressure keep negative pressure state, then close argon gas valve 4.Set induction heating power and heating frequency, open induction heating device 1, by controlling energy input, sample temperature is controlled within the scope of the one-tenth phase temperature range of 1:13 phase.Reach after the specified time, stop heating, be filled with argon gas cooling.To be cooled to room temperature, open sample chamber, take out sample.
Embodiment 1:
Adopt LaFe
11.5si
1.5magnetic refrigerating material, thickness of sample 2mm, adopts 300kHz × 10kW, adopts pulse heating mode (conduction time T
1=12s, power-off time T
2=2s), heating 60min, then, logical argon gas is cooling, obtains the material LaFe with 1:13 phase
11.5si
1.5magnetic refrigerating material.
Embodiment 2:
Adopt LaFe
11.2si
1.8magnetic refrigerating material, thickness of sample 1mm, adopts 500kHz × 15kW, adopts pulse heating mode (conduction time T
1=10s, power-off time T
2=2s), heating 20min, then, logical argon gas is cooling, obtains the material LaFe with 1:13 phase
11.2si
1.8magnetic refrigerating material.
Embodiment 3:
Adopt La
0.8pr
0.2fe
11.5si
1.5magnetic refrigerating material, thickness of sample 2mm, adopts 500Hz × 10kW, adopts pulse heating mode (conduction time T
1=12s, power-off time T
2=2s), heating 35min, then, logical argon gas is cooling, obtains the material La with 1:13 phase
0.8pr
0.2fe
11.5si
1.5magnetic refrigerating material.
Embodiment 4:
Adopt La
0.9ce
0.1fe
10.8co
0.7si
1.5magnetic refrigerating material, thickness of sample 0.5mm, adopts 60Hz × 50kW, adopts pulse heating mode (conduction time T
1=20s, power-off time T
2=1s), heating 55min, then, logical argon gas is cooling, obtains the material La with 1:13 phase
0.9ce
0.1fe
10.8co
0.7si
1.5magnetic refrigerating material.
Embodiment 5:
Adopt LaFe
10.8co
0.7si
1.5c
0.2magnetic refrigerating material, thickness of sample 0.5mm, adopts 400kHz × 30kW, adopts pulse heating mode (conduction time T
1=8s, power-off time T
2=4s), heating 45min, then, logical argon gas is cooling, obtains the material LaFe with 1:13 phase
10.8co
0.7si
1.5c
0.2magnetic refrigerating material.
embodiment 6
Adopt LaFe
10.8co
0.7si
1.5magnetic refrigerating material, thickness of sample 2mm, its as-cast structure is as shown in Figure 2.Adopt 300kHz × 100kW, adopt pulse heating mode (conduction time T
1=2s, power-off time T
2=1s), heating 20min, then, logical argon gas is cooling, obtains the material LaFe with 1:13 phase
10.8co
0.7si
1.5magnetic refrigerating material, its microtexture as shown in Figure 3.
embodiment 7
Adopt LaFe
10.8co
0.7si
1.5c
0.2magnetic refrigerating material, thickness of sample 2mm, its as-cast structure is as shown in Figure 4.Adopt 100kHz × 20kW, adopt pulse heating mode (conduction time T
1=10s, power-off time T
2=8s), heating 30min, then, logical argon gas is cooling, obtains the material LaFe with 1:13 phase
10.8co
0.7si
1.5c
0.2magnetic refrigerating material, its microtexture photo as shown in Figure 5.
embodiment 8
Adopt LaFe
10.8co
0.7si
1.5c
0.2magnetic refrigerating material, thickness of sample 2mm, adopts 1kHz × 60kW, adopts pulse heating mode (conduction time T
1=6s, power-off time T
2=2s), heating 10min, then, logical argon gas is cooling, obtains the material LaFe with 1:13 phase
10.8co
0.7si
1.5c
0.2magnetic refrigerating material, its microtexture photo as shown in Figure 6.
Claims (1)
1.
a kind ofpreparation Ln (Fe, M)
13be the method for magnetic refrigerating material, it is characterized in that, specifically comprise following technique: by thickness sheet Ln (Fe, M) between 0.5-2mm
13be magnetic refrigerating material, put into sample chamber, adopt pulse heating mode, first vacuumize, when vacuum tightness reaches 2.0 × 10
-3pa, is filled with argon shield, is 60Hz-500kHz in frequency, and power is 10-100kW, conduction time T
1=2-20s, power-off time T
2=1-8s, heating 10-60 minute, then pass into argon gas cooling after, obtain and there is the sheet Ln (Fe, M) of 1:13 phase
13it is magnetic refrigerating material.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210371325.1A CN102828107B (en) | 2012-09-28 | 2012-09-28 | Preparation method and device for Ln(Fe,M)13 series magnetic refrigeration materials |
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|---|---|---|---|
| CN201210371325.1A CN102828107B (en) | 2012-09-28 | 2012-09-28 | Preparation method and device for Ln(Fe,M)13 series magnetic refrigeration materials |
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|---|---|
| CN102828107A CN102828107A (en) | 2012-12-19 |
| CN102828107B true CN102828107B (en) | 2014-08-13 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108467928B (en) * | 2018-03-02 | 2020-01-10 | 横店集团东磁股份有限公司 | Method for improving half-height width of magnetic entropy variation curve of LaFeSi alloy magnetic refrigeration material |
| CN111072063A (en) * | 2018-10-22 | 2020-04-28 | 天津理工大学 | Perovskite rare earth metal oxide low-temperature magnetic refrigeration material and preparation method thereof |
| CN114058798B (en) * | 2021-11-26 | 2023-07-14 | 上海大学 | Flash annealing process and device for La-Fe-Si alloy |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101748326A (en) * | 2009-10-19 | 2010-06-23 | 北京科技大学 | Preparation method of carbonic rare earth-ferrum, cobalt and silicon compound with NaZn1 structure |
| CN102179502A (en) * | 2011-04-26 | 2011-09-14 | 北京科技大学 | Device and method for preparing metal matrix composite by adopting high-pressure gas to assist infiltration |
-
2012
- 2012-09-28 CN CN201210371325.1A patent/CN102828107B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101748326A (en) * | 2009-10-19 | 2010-06-23 | 北京科技大学 | Preparation method of carbonic rare earth-ferrum, cobalt and silicon compound with NaZn1 structure |
| CN102179502A (en) * | 2011-04-26 | 2011-09-14 | 北京科技大学 | Device and method for preparing metal matrix composite by adopting high-pressure gas to assist infiltration |
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